CN115318341B - Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof - Google Patents

Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof Download PDF

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CN115318341B
CN115318341B CN202211049796.0A CN202211049796A CN115318341B CN 115318341 B CN115318341 B CN 115318341B CN 202211049796 A CN202211049796 A CN 202211049796A CN 115318341 B CN115318341 B CN 115318341B
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bimetallic mof
heterogeneous catalyst
bimetallic
imidazole
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CN115318341A (en
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刘少青
李云肸
陈瑶
范闽光
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Guangxi University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Abstract

The invention discloses an imidazole functionalized bimetallic MOF heterogeneous catalyst with a relatively complete octahedral crystal structure, and the preparation method comprises the following operation steps: (1) preparing an ionic liquid; (2) preparing a bimetallic MOF material; (3) Mixing the ionic liquid with the bimetallic MOF material, refluxing, cooling, centrifuging, and drying the solid obtained after centrifuging to obtain the imidazole functionalized bimetallic MOF heterogeneous catalyst. The catalyst of the invention has three active centers of bimetallic active sites and halogen anions, utilizes the coordination of the empty orbit of unsaturated metal and the carboxyl of the ionic liquid to form stable coordination, and simultaneously the coordination increases the recycling property of the catalyst; therefore, the content ratio of the unsaturated metal to the ionic liquid is a key point for preparing the efficient catalyst, and the mol ratio of the two metals is limited, so that the bimetal achieves a powerful balance in a competitive scene, thereby relatively improving the reactivity.

Description

Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof
Technical Field
The invention belongs to the field of heterogeneous catalysis and organic material preparation, and particularly relates to an imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof.
Background
The excessive utilization of mineral resources such as coal, natural gas, petroleum and the like in daily life leads to remarkable increase of carbon emission, forms a series of serious threats such as global warming and resource shortage to ecological environment, and carbon dioxide as a C1 structural unit has wide application in synthesizing valuable chemicals and energy products. Thus, the elimination of carbon dioxide emissions over standard and the conversion of carbon dioxide into other valuable chemicals are an urgent research project driven by sustainable resource and environmental protection concepts.
CO 2 Reaction with epoxide can produce cyclic carbonate with 100% atom economy efficiency, which is the effect of carbon dioxide conversion at this stageThe effective way. Cyclic carbonates are widely used as electrolytes in lithium ion batteries, precursors and intermediates for polymerization and organic reactions, and aprotic solvents in chemical synthetic pathways, due to their good biodegradability, high solubility, high dielectric constant, low volatility, etc. Although cycloaddition reaction of carbon dioxide and epoxide has been developed to be mature, the problems of high production cost, complex synthesis process, harsh reaction conditions and the like still exist. Considering that higher activation energy is required for carbon dioxide activation, the catalyst is a necessary bridge for cyclic carbonate conversion. Thus, the development of a heterogeneous catalyst with excellent catalytic yields, high selectivity, ease of separation and high circulation is still a struggle goal for current researchers.
Catalysts developed and utilized at present mainly comprise heterogeneous catalysts such as ionic liquid homogeneous catalysts and metal organic frameworks. Wherein, ionic liquid is popular because it contains both anions and cations and can be co-catalyzed in the reaction system. However, ionic liquids are often limited by complex preparation processes, harsh reaction conditions, and difficulty in separation. In addition, heterogeneous catalysts represented by metal organic frameworks MOFs, which have a high content of metal active sites, structural adjustability and ease of separation, are widely used. However, due to its poor stability, the recycling rate is generally low. Therefore, there remains a need to develop an efficient and economical imidazole functionalized bimetallic MOF heterogeneous catalyst that is expected to have better effect in cycloaddition reactions.
Disclosure of Invention
Aiming at the technical problems, the invention discloses an imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof, so as to solve the problems of poor activity, poor stability, severe catalytic conditions, difficult recycling and the like of the existing catalyst.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
an imidazole functionalized bimetallic MOF heterogeneous catalyst having the following properties: the imidazole functionalized bimetallic MOF heterogeneous catalyst is a MIL-101 series metal organic framework and has a relatively complete octahedral crystal structure.
The preparation method of the imidazole functionalized bimetallic MOF heterogeneous catalyst comprises the following operation steps:
(1) Preparing an ionic liquid: under the condition that toluene is taken as a solvent, 1-methylimidazole and 3-bromopropionic acid reflux overnight under nitrogen, so as to obtain a carboxyl imidazolium ionic liquid containing coordination;
(2) Preparing a bimetallic MOF material: chromium nitrate nonahydrate (Cr (NO) 3 ) 3 ·9H 2 O), nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O), terephthalic acid (H) 2 BDC，C 8 H 6 O 4 ) Dissolving in water, adding hydrofluoric acid (HF), dissolving, performing hydrothermal reaction, cooling to room temperature, centrifuging to obtain crude product, refluxing in N, N-Dimethylformamide (DMF) solvent for 1 time, refluxing with anhydrous ethanol, centrifuging the obtained solution, drying the bottom solid after centrifuging, and grinding to obtain catalyst MIL-101 (Cr/Ni) a-b (a-b is Cr (NO) 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 O mole ratio), soaking in methanol solution, drying in an oven, and grinding to obtain the bimetallic MOF material;
(3) Mixing the ionic liquid prepared in the step (1) with the bimetallic MOF material prepared in the step (2), refluxing, cooling, centrifuging, and drying the solid obtained after centrifuging to obtain the imidazole functionalized bimetallic MOF heterogeneous catalyst.
Preferably, the ionic liquid prepared in the step (1) is more specifically prepared by the following steps: dissolving 1-methylimidazole and 3-bromopropionic acid in toluene solution in a molar ratio of 1:1, stirring the mixture at normal temperature by ultrasonic to completely dissolve the mixture, continuously stirring the obtained mixed solution at 110 ℃ for 5 hours under the protection of nitrogen, washing the obtained product to obtain suspension, evaporating toluene solvent to obtain light yellow oily liquid, repeating the operation of rinsing and rotary evaporation for 3 times, and finally drying the obtained substance to obtain the complexable carboxyimidazolium-containing ionic liquid.
Preferably, the washing is performed by washing with hot acetonitrile at 70 ℃ and then rinsing with dichloromethane; the drying is carried out at 80 ℃ for 12 hours.
Preferably, the hydrothermal reaction in the step (2) is carried out at 220 ℃ for 8 hours; refluxing in the step (2) in N, N-Dimethylformamide (DMF) solvent at 130 ℃ for 12h, repeating the refluxing operation for 1 time, and then adding absolute ethanol and refluxing at 80 ℃ for 24h.
Preferably, chromium nitrate nonahydrate in step (2) (Cr (NO) 3 ) 3 ·9H 2 O), nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O) is added in a molar ratio of 1:3; and (3) soaking in the methanol solution for 12 hours in the step (2), and then drying in an oven.
Preferably, in step (3), the mixture is refluxed at 130 ℃ for 24 hours; in the step (3), the ionic liquid and the bimetallic MOF material are mixed in a molar ratio of 4:1.
Use of an imidazole functionalized bimetallic MOF heterogeneous catalyst as described above in a carbon dioxide cycloaddition reaction.
As applied above, the method of operation is: at 60 ℃, imidazole functionalized bimetallic MOF heterogeneous catalyst and epoxide are added, and carbon dioxide is introduced to carry out cycloaddition reaction to obtain the cyclic carbonate with higher content.
Preferably, the reaction time is 3h, and the initial pressure of carbon dioxide is 1.2MPa; the epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, allyl glycidyl ether and epoxycyclohexane.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst of the invention has three active centers of bimetallic active sites and halogen anions, utilizes the coordination of the empty orbit of unsaturated metal and the carboxyl of the ionic liquid to form stable coordination, and simultaneously the coordination increases the recycling property of the catalyst; therefore, the content ratio of the unsaturated metal to the ionic liquid is the key for preparing the efficient catalyst, and the mol ratio of the two metals is limited, so that the bimetal achieves a powerful balance in a competitive scene, thereby relatively improving the reactivity; furthermore, the catalyst provided by the invention has excellent catalytic performance in the application of the carbon dioxide cycloaddition reaction, solves the problem that the existing catalyst can only convert carbon dioxide under the high-temperature condition, and reduces the condition of chemical reaction by utilizing the composite material coordinated by the bimetallic ionic liquid.
Drawings
FIG. 1 shows an ImBr ionic liquid according to the invention 1 H NMR spectrum.
Figure 2 is an XRD pattern of the imidazole functionalized bimetallic MOF heterogeneous catalyst of the present invention.
FIG. 3 shows the bimetallic MOF material (MIL-101 (Cr/Ni) prepared in step (2) of example 1 1-3 ) Is magnified 500nm.
FIG. 4 shows an imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in example 1 1-3 -ImBr), 500nm magnification.
FIG. 5 shows a bimetallic MOF material (MIL-101 (Cr/Ni) prepared in comparative example 2 1-1 ) Is magnified 500nm.
FIG. 6 comparative example 3 MIL-101 (Cr/Ni) obtained 3-1 Is magnified 500nm.
Detailed Description
The following detailed description, in conjunction with the accompanying drawings, describes in detail, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were commercially available unless otherwise specified.
Example 1
An imidazole functionalized bimetallic MOF heterogeneous catalyst having the following properties: the imidazole functionalized bimetallic MOF heterogeneous catalyst is a MIL-101 series metal organic framework and has a relatively complete octahedral crystal structure.
The preparation method of the imidazole functionalized bimetallic MOF heterogeneous catalyst comprises the following operation steps:
(1) Preparing an ionic liquid: dissolving 3.32mL of 1-methylimidazole (40 mmol) and 6.12g of 3-bromopropionic acid (40 mmol) in 70mL of toluene solution, stirring for 10min at normal temperature to completely dissolve the solution, transferring the obtained mixed solution into a 100mL three-necked round bottom flask, continuously stirring for 5h at 110 ℃ under the protection of nitrogen, flushing the obtained product with hot acetonitrile at 70 ℃, then rinsing with dichloromethane, removing the toluene solvent from the obtained suspension through rotary evaporation to obtain light yellow oily liquid, repeating the operation of rinsing and rotary evaporation for 3 times, and finally drying the obtained substance at 80 ℃ for 12h to obtain the complexable carboxyimidazolium-containing ionic liquid, which is marked as ImBr;
(2) Preparing a bimetallic MOF material: 4g of Cr (NO) 3 ) 3 ·9H 2 O (10 mmol), 8.72g Ni (NO) 3 ) 2 ·6H 2 O (30 mmol), 1.66g H 2 BDC(C 8 H 6 O 4 Dissolving 10mmol in 45mL deionized water, adding 0.2mL fluorous acid, stirring at room temperature for 3h ultrasonic dissolution, transferring the solution into a 100mL brown polytetrafluoroethylene lining, loading into a kettle, placing in a 220 ℃ oven for hydrothermal reaction for 8h, cooling to room temperature, taking out the obtained suspension after reaction, centrifuging the suspension in a centrifuge at 8500r/min for 8min to obtain a solid, dissolving the obtained solid and a three-necked flask containing 80mL DMF (N, N-dimethylformamide) by ultrasonic treatment to completely dissolve the obtained solid, then refluxing at 130 ℃ for 12h, refluxing for 1 time (namely refluxing for 2 times), changing the solution into absolute ethyl alcohol at 80 ℃ for 24h (the original solution is DMF, changing the original solution into absolute ethyl alcohol), centrifuging the obtained solution, taking the bottom solid after centrifugation, drying at 100 ℃ for 24h, and fully grinding to obtain the catalyst MIL-101 (Cr/Ni) 1-3 Soaking in methanol solution for 12 hr, drying in oven for 24 hr, and grinding to obtain solid powder, which is bimetallic MOF material (MIL-101 (Cr/Ni) 1-3 )；
(3) Dissolving 1.2mL of the ionic liquid prepared in the step (1) and 1g of the bimetallic MOF material prepared in the step (2) in a molar ratio of 4:1 in a three-necked flask filled with 50mL of DMF, refluxing for 24h at 130 ℃, cooling, centrifuging, drying the solid obtained after centrifuging in a vacuum oven at 80 ℃ for 12h, and fully grinding to obtain the imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) 1-3 -ImBr)。
Comparative example 1
The catalyst MIL-101 (Cr/Ni) obtained in step (2) of example 1 was sufficiently ground 1-3 Is placed atSoaking in methanol solvent for 24 hr and 48 hr respectively, drying the soaked materials in oven, and grinding to obtain bimetal MOF material (MIL-101 (Cr/Ni) 1-3 ) And (5) standby.
Comparative example 2
(2) Preparing a bimetallic MOF material: taking Cr (NO) 3 ) 3 ·9H 2 O(4g,10mmol)、Ni(NO 3 ) 2 ·6H 2 O(2.91g,10mmol)、H 2 BDC(C 8 H 6 O 4 10mmol,1.66 g) was dissolved in 45mL deionized water and the remainder was the same as in step (2) of example 1 to prepare a bimetallic MOF material (MIL-101 (Cr/Ni) 1-1 )。
Comparative example 3
(2) Preparation of catalyst MIL-101 (Cr/Ni) 3-1 Materials: taking Cr (NO) 3 ) 3 ·9H 2 O(4g,10mmol)、Ni(NO 3 ) 2 ·6H 2 O(8.72g,30mmol)、H 2 BDC(C 8 H 6 O 4 10mmol,1.66 g) was dissolved in 45mL deionized water and the rest was the same as in step (2) of example 1 to give catalyst MIL-101 (Cr/Ni) 3-1 。
Comparative example 4
The bimetallic MOF material (MIL-101 (Cr/Ni) prepared in comparative example 2 was taken 1-1 ) 1.05mL of the ionic liquid obtained in the step (1) of example 1 was dissolved in a three-necked flask containing 50mL of DMF, and the other operations were the same as in the step (3) of example 1 to obtain an imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) 1-1 -ImBr)。
Comparative example 5
MIL-101 (Cr/Ni) obtained in comparative example 3 was obtained 3-1 1.1mL of the ionic liquid obtained in the step (1) of example 1 was dissolved in a three-necked flask containing 50mL of DMF, and the other operations were the same as in the step (3) of example 1 to obtain an imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) 3-1 -ImBr)。
Application example 1
Three different time methanol solutions prepared in example 1, step (2) and comparative example 1 were taken respectivelyThe catalyst bimetallic MOF material (MIL-101 (Cr/Ni)) obtained after treatment 1-3 ) 100mg of substrate epoxide propylene oxide 34.5mmol is added into a 50mL high-pressure reaction kettle and 1.2MPa CO is filled in 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas, and sampling for analysis by gas chromatography; the results show that the catalyst bimetallic MOF material obtained in step (2) of example 1 (MIL-101 (Cr/Ni) 1-3 12h methanol solution treatment) was 70% with 89% selectivity; the bimetallic MOF material of the catalyst obtained in comparative example 1 (MIL-101 (Cr/Ni) 1-3 24h methanol solution treatment) was 75% and the selectivity was 92%; the bimetallic MOF material of the catalyst obtained in comparative example 1 (MIL-101 (Cr/Ni) 1-3 48h methanol solution treatment) was 53% (conversion of epoxide to cyclic carbonate, the same applies below) and the selectivity was 80%.
Application example 2
Taking imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in example 1 1-3 -ImBr) 100mg, 34.5mmol of substrate propylene oxide, are charged into a 50mL autoclave, filled with 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas to obtain higher-content cyclic carbonate, and sampling and analyzing by gas chromatography; the results showed 94.8% conversion and 99% selectivity.
Application example 3
The imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in comparative example 4 was taken 1-1 -ImBr) 100mg, 34.5mmol of substrate propylene oxide, are charged into a 50mL autoclave, filled with 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas, and sampling for analysis by gas chromatography; the results showed 84.5% conversion and 98.9% selectivity.
Application example 4
Get the comparison of the realEXAMPLE 5 preparation of the resulting imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) 3-1 -ImBr) 100mg, 34.5mmol of substrate propylene oxide, are charged into a 50mL autoclave, filled with 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas, and sampling for analysis by gas chromatography; the results showed 68.8% conversion and 98.6% selectivity. .
In summary, the imidazole functionalized bimetallic MOF heterogeneous catalyst prepared in example 1 was selected for use (MIL-101 (Cr/Ni) 1-3 ImBr) to explore its applicability.
Application example 5
Taking imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in example 1 1-3 -ImBr) 100mg, 34.5mmol of the substrate epichlorohydrin, was charged into a 50mL autoclave, and 1.2MPa CO was charged 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas, and sampling for analysis by gas chromatography; the results showed 95.0% conversion and 99% selectivity.
Application example 6
Taking imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in example 1 1-3 -ImBr) 100mg, 34.5mmol of substrate styrene oxide, was charged into a 50mL autoclave, and 1.2MPa CO was charged 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas, and sampling for analysis by gas chromatography; the result showed 83.3% conversion and 98.8% selectivity.
Application example 7
Taking imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in example 1 1-3 -ImBr) 100mg, 34.5mmol of the substrate allyl glycidyl ether, are charged into a 50mL autoclave and 1.2MPa CO is charged 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, and then naturally cooling the reaction kettleReleasing unreacted gas to room temperature, and sampling and analyzing by gas chromatography; the results showed 82.5% conversion and 98.3% selectivity.
Application example 8
Taking imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) prepared in example 1 1-3 -ImBr) 100mg, 34.5mmol of substrate epoxycyclohexane, are charged into a 50mL autoclave, filled with 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas, and sampling for analysis by gas chromatography; the results showed a conversion of 8.7% and a selectivity of 98.0%.
Application example 9
Taking the solid after the reaction of application example 2 (namely the catalyst used in application example 2), washing twice with acetone, drying for 12 hours at 80 ℃ in an oven, adding 30.5mmol of substrate propylene oxide into a 50mL high-pressure reaction kettle after grinding sufficiently, and filling 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas to obtain higher-content cyclic carbonate, and sampling and analyzing by gas chromatography; the results showed 94.3% conversion and 99.2% selectivity.
Application example 10
Taking the solid after the reaction of application example 9 (namely the catalyst used in application example 9), washing twice with acetone, drying for 12 hours at 80 ℃ in an oven, adding 26.7mmol of substrate propylene oxide into a 50mL high-pressure reaction kettle after grinding sufficiently, and filling 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas to obtain higher-content cyclic carbonate, and sampling and analyzing by gas chromatography; the results showed 94.0% conversion and 99% selectivity.
Application example 11
Taking the solid after the reaction of application example 10 (namely the catalyst used in application example 10), washing twice with acetone, drying for 12 hours at 80 ℃ in an oven, grinding thoroughly, and then adding a substrate propylene oxide24mmol is added into a 50mL high-pressure reaction kettle and 1.2MPa CO is filled in 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas to obtain higher-content cyclic carbonate, and sampling and analyzing by gas chromatography; the results showed 93.6% conversion and 98.6% selectivity.
Application example 12
Taking the solid after the reaction of application example 11 (namely the catalyst used in application example 11), washing twice with acetone, drying for 12 hours at 80 ℃ in an oven, adding 20.6mmol of substrate propylene oxide into a 50mL high-pressure reaction kettle after grinding sufficiently, and filling 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas to obtain higher-content cyclic carbonate, and sampling and analyzing by gas chromatography; the results showed 93.0% conversion and 98.4% selectivity.
Application example 13
Taking the solid after the reaction of application example 12 (namely the catalyst used in application example 11), washing twice with acetone, drying for 12 hours at 80 ℃ in an oven, adding 18.8mmol of substrate propylene oxide into a 50mL high-pressure reaction kettle after grinding sufficiently, and filling 1.2MPa CO 2 Placing the high-pressure reaction kettle in a constant-temperature heating sleeve, heating to 60 ℃, reacting for 3 hours, naturally cooling the reaction kettle to room temperature, releasing unreacted gas to obtain higher-content cyclic carbonate, and sampling and analyzing by gas chromatography; the results showed 92.4% conversion and 98.0% selectivity.
Several different catalysts were prepared according to the procedure of step (1) of example 1, and this was characterized in relation. Example 1 Ionic liquid ImBr prepared in step (1) 1 The H NMR spectrum is shown in fig. 1: characteristic signals at 8.71ppm and 7.45ppm indicate the presence of an imidazole ring, and the peak of alkyl hydrogen at 2.92ppm makes its chemical shift smaller due to electron withdrawing action of carboxyl group, thus indicating successful ionic liquid synthesis.
EXAMPLE 1 step (2) the resulting bimetallic MOF material (MIL-101 (Cr/Ni) 1-3 ) The bimetallic MOF material prepared in comparative examples 1-3, the imidazole functionalized bimetallic MOF heterogeneous catalyst prepared in step (3) of example 1 (MIL-101 (Cr/Ni) 1-3 ImBr) and simulated MILs-101X-ray diffraction patterns are shown in fig. 2 (simulated MILs-101 refers to a standard XRD pattern simulated from the crystal database in the literature): from the XRD diffraction patterns, it can be seen that the main diffraction peaks of 5.78 °, 9.04 °, 16.60 ° and 18.86 ° are consistent with the simulated peaks of MIL-101, indicating that the samples prepared in each example are assigned to the MIL-101 series of metal-organic frameworks. No new peaks appear from the spectra, particularly like metal Ni and metal oxide peaks, indicating that the doping of the metal source Ni does not affect the change of the lattice. However, the intensity of the peaks was changed, possibly due to the difference in atomic radii of Cr and Ni, in relation to the molar ratio, indirectly indicating successful doping of metallic Ni. In particular MIL-101 (Cr/Ni) 1-3 ImBr compared to MIL-101 (Cr/Ni) 1-3 The peak at 8.98 deg. shifted, which is shown at 9.7 deg., indicating that the ionic liquid ImBr was successfully grafted onto this metal organic framework.
EXAMPLE 1 step (2) the resulting bimetallic MOF material (MIL-101 (Cr/Ni) 1-3 ) EXAMPLE 1 step (3) imidazole functionalized bimetallic MOF heterogeneous catalyst (MIL-101 (Cr/Ni) 1-3 ImBr), bimetallic MOF material obtained in comparative example 2 (MILs-101 (Cr/Ni) 1-1 ) Comparative example 3 the bimetallic MOF material obtained (MIL-101 (Cr/Ni) 3-1 ) The scanning electron microscope of (2) is shown in fig. 3: from the figure, it can be seen that the bimetallic MOF material (MIL-101 (Cr/Ni) prepared in step (2) of example 1 1-3 ) Has a more complete octahedral crystal structure, and the imidazole functionalized bimetallic MOF heterogeneous catalyst prepared in step (3) of example 1 (MIL-101 (Cr/Ni) 1-3 ImBr) on the basis of an octahedral structure, which can be successfully attributed on the one hand to the grafting of ionic liquids and on the other hand is advantageous for the transport and reaction of the reaction medium. Comparative example 2 the bimetallic MOF material (MIL-101 (Cr/Ni) 1-1 ) Has become an unfilled octahedron, not a perfect configuration, resulting in contact of the active medium that is notAs a perfect crystal. Comparative example 3 preparation of the obtained bimetallic MOF Material (MIL-101 (Cr/Ni) 3-1 ) The graph of (2) shows that there is no particular morphology, and that bulk stacking results in a significant reduction in specific surface area and is detrimental to carbon dioxide adsorption.
As shown by the results obtained in application examples 2, 3 and 4, three different catalysts were used to catalyze the cycloaddition of carbon dioxide with epoxide, MIL-101 (Cr/Ni) 1-3 ImBr has the highest conversion and selectivity, whereas MIL-101 (Cr/Ni) 3-1 ImBr has low conversion and yield, probably due to MILs-101 (Cr/Ni) 1-3 ImBr has a good crystal structure and surface roughness provides convenient conditions for transport of reactants and reaction media. In addition, MIL-101 (Cr/Ni) is adopted in the invention 1-3 ImBr applied to different epoxides, a rule of activity was found, with the order of yields of epichlorohydrin<Propylene oxide<Styrene oxide, allyl glycidyl ether<Epoxycyclohexane. This is mainly due to steric hindrance and the action of electron withdrawing groups, and the test results for different conditions and different epoxides are shown in tables 1, 2.
TABLE 1 cycloaddition reaction results of different catalysts for propylene oxide
Sample of Yield (%) Selectivity (%)
MIL-101(Cr/Ni) 1-3 12h (example 1 step (2)) 70.0 89.0
MIL-101(Cr/Ni) 1-3 24h (comparative example 1) 75.0 92.0
MIL-101(Cr/Ni) 1-3 48h (comparative example 1) 53.0 80.0
MIL-101(Cr/Ni) 1-3 ImBr (example 1) 94.3 99.2
MIL-101(Cr/Ni) 1-1 ImBr (comparative example 4) 84.5 98.9
MIL-101(Cr/Ni) 3-1 ImBr (comparative example 5) 68.8 98.9
TABLE 2 catalytic results for different epoxides
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (7)

1. The imidazole functionalized bimetallic MOF heterogeneous catalyst is characterized in that the imidazole functionalized bimetallic MOF heterogeneous catalyst is a MIL-101 series metal organic framework and has a complete octahedral crystal structure; the preparation method of the imidazole functionalized bimetallic MOF heterogeneous catalyst comprises the following operation steps:
(1) Preparing an ionic liquid: under the condition that toluene is taken as a solvent, 1-methylimidazole and 3-bromopropionic acid reflux overnight under nitrogen, so as to obtain a carboxyl imidazolium ionic liquid containing coordination;
(2) Preparing a bimetallic MOF material: dissolving chromium nitrate nonahydrate, nickel nitrate hexahydrate and terephthalic acid in water, adding hydrofluoric acid, dissolving, performing hydrothermal reaction, cooling to room temperature, centrifuging to obtain a crude product, refluxing in an N, N-dimethylformamide solvent, adding ethanol, refluxing, centrifuging the obtained solution, drying the solid at the bottom after centrifuging, and sufficiently grinding to obtain the catalyst MIL-101 (Cr/Ni) a-b Soaking in methanol solution for 12h, drying, and grinding to obtain bimetal MOF material; the chromium nitrate nonahydrate and the nickel nitrate hexahydrate are added in the molar ratio of 1:3; wherein a-b are Cr (NO 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 Molar ratio of O;
(3) Mixing the ionic liquid prepared in the step (1) and the bimetallic MOF material prepared in the step (2) in a molar ratio of 4:1, refluxing for 24h at 130 ℃, cooling, centrifuging, and drying the solid obtained after centrifuging to obtain the imidazole functionalized bimetallic MOF heterogeneous catalyst.
2. The imidazole-functionalized bimetallic MOF heterogeneous catalyst of claim 1, wherein: the more specific operation of the ionic liquid preparation in the step (1) is as follows: dissolving 1-methylimidazole and 3-bromopropionic acid in toluene solution in a molar ratio of 1:1, stirring by ultrasonic to completely dissolve the solution, continuously stirring the obtained mixed solution at 110 ℃ for 5 hours under the protection of nitrogen, washing the obtained product to obtain suspension, evaporating toluene solvent to remove the toluene solvent to obtain light yellow oily liquid, repeatedly rinsing and rotary evaporating, and finally drying the obtained substance to obtain the carboxyl imidazolium ionic liquid containing coordination.
3. The imidazole-functionalized bimetallic MOF heterogeneous catalyst according to claim 2, characterized in that: the washing is to wash with hot acetonitrile at 70 ℃ and then rinse with dichloromethane; the drying is to dry 12h at 80 ℃.
4. The imidazole-functionalized bimetallic MOF heterogeneous catalyst of claim 1, wherein: the hydrothermal reaction in the step (2) is carried out for 8 hours at 220 ℃; in the step (2), the mixture is refluxed at 130 ℃ in an N, N-dimethylformamide solvent, and then ethanol is added to reflux at 80 ℃ for 24h.
5. Use of an imidazole functionalized bimetallic MOF heterogeneous catalyst according to any one of claims 1-4 in a carbon dioxide cycloaddition reaction.
6. The application according to claim 5, wherein the application operation method is: at 60 ℃, imidazole functionalized bimetallic MOF heterogeneous catalyst and epoxide are added, and carbon dioxide is introduced to carry out cycloaddition reaction to obtain the cyclic carbonate with higher content.
7. The use according to claim 6, characterized in that: the reaction time is 3 hours, and the initial pressure of carbon dioxide is 1.2MPa; the epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, allyl glycidyl ether and epoxycyclohexane.
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